Infrared reflecting layer system for transparent substrate

ABSTRACT

An infrared radiation reflecting transparent layer system on a transparent substrate and a method for producing same is provided. The infrared radiation reflecting layer system comprises an infrared radiation reflecting layer sequence which includes a selective function usually consisting of a noble metal, mostly silver, or an alloy thereof and having a good selective reflectivity in the infrared range. The layer sequence is supplemented by at least one transparent dielectric layer of an oxynitride of a metal, a semiconductor or a semiconductor alloy having a low to moderate refractive index arranged directly on the substrate or above the infrared radiation reflecting layer sequence.

CROSS-REFERENCE TO RELATED APPLICATION

The instant application claims the benefit of prior German PatentApplication No. DE 10 2006 024 524.5 filed on May 23, 2006, which isincorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates to an infrared radiation reflecting layersystem on a transparent substrate having a sequence of layers that areapplied to the substrate and reflect infrared radiation. The sequence oflayers includes at least one selective function layer.

The invention also relates to a method for manufacturing such a layersystem in which an infrared radiation reflecting layer sequence isapplied to a transparent substrate by a suitable method.

In general, an infrared radiation reflecting layer system (low-E layersystem) comprises the function layer, a base layer that improvesadhesion of the function layer and a reflection reducing top layer,whereby the individual layers may repeat within the layer system. Thefunction layer, usually consisting of a noble metal, mostly silver, oran alloy thereof, has a good selective reflectivity in the infraredrange even with a small layer thickness. If only one function layer isarranged in the layer system, this is often referred to as a “singlelow-E” system.

The top layer also serves to improve the mechanical and chemicalstability, in addition to reducing reflection. It is usually made of ahighly refractive dielectric material containing silicon. To increasethe transmittance of the layer system in the visible range, thesereflection-reducing layers are arranged above and beneath the selectivefunction layer.

Such infrared radiation reflecting transparent layer systems are alsosubjected to tempering processes to harden and/or shape the substrate.In this case they have a layer sequence having layer properties suchthat a substrate having this layer system may be subjected to a heattreatment and any changes that occur in the optical, mechanical andchemical properties of the layer system may be kept within definedlimits. Depending on the application of a coated substrate, its layersystem is exposed to different climate conditions in different timeregimens during the tempering process.

Because of different thermal loads to which the layer sequences alreadyapplied are subjected, various processes that alter the reflectivity ofthe function layer and the transmittance of the layer system occur inthe course of production of the following layers of the layer system andthe tempering process, in particular diffusion of components of thereflection reducing layer into the function layer and vice versa. Toprevent such diffusion processes, a blocking layer that serves as abuffer for the diffusing components is inserted between thereflection-reducing layer and the function layer. These blocking layersare structured and arranged according to the thermal burden that occursand protect the sensitive function layer, which is often very thin orthe function layers from the influence of neighboring layers. Inparticular shifts in color of the layer system and an increase insurface resistance of the layer system due to the tempering process areprevented by the introduction of one or more blocking layers.

In particular NiCr or NiCrO_(x) layers are known as blocking layers fortemporable layer systems. For example DE 035 43 178 and EP 1 174 379describe blocking layers which include silver layer(s) or at leastprotect them on one side. However, the blocking layers cause a reductionin conductivity of the silver layer(s). If a silver layer with a surfaceresistance of approx. 5 ohm/sq. is deposited and embedded in twoNiCrO_(x) layers, this embedding may lead to an increase in the surfaceresistance by approx. 1.5 ohm/sq. to 6.5 ohm/sq. [sic].

EP 0 999 192 B1 describes a layer system including a silver layer as aselective function layer which is provided with a blocking layer ofnickel or nickel chromium on both sides. By introducing an NiCrO_(x)layer into the functional silver layer in a single low E system, thelayer system is stabilized in the heat treatment. The disadvantage isthat with this layer system, each individual layer of the two silverpartial layers must be approximately 7 to 8 nm thick to prevent theformation of islands with the silver partial layers. This in turn leadsto a low transmittance of the layer system. Furthermore, EP 0 999 192 B1discloses the use of a substoichiometric TiO_(x) layer between theblocking layer and the silver layer, which should reduce the so-calledhaze formation, i.e., the change in optical properties of the functionlayer due to diffusion processes into the function layer. However, thisabsorbent TiO_(x) layer undergoes oxidation during the heat treatment,resulting in significant changes in the transmittance and a shift in thepreset color locus.

EP 1 238 950 A2 discloses a temperable layer system that is providedwith NiCrO_(x) layers as blocking layers on both sides of a silver layeras the sensitive layer.

Furthermore, dielectric interface layers are provided in this layersystem and are situated above and below the blocking layers. Such layershave various stabilizing effects on the layer system and also act as adiffusion barrier during the tempering processes.

Furthermore, EP 1 238 950 describes the use of gradient layers instabilization of heat-treatable layer systems. The disadvantage here isthat the SiN_(x) layer is beneath the blocking layer so that theelectric surface resistance and thus the emissivity of the layer systemare not reduced. In this approach, several layer sequences of sensitivesilver layers with underlayers and two blocking layers enclosing therespective silver layer are provided.

DE 100 46 810 also discloses the application of metallic blocking layerswhich form a gradient layer with the silver as the function layer in atransitional area between the two layers. The reflection-reducing layermay also consist of several metal oxide layers with a gradient layerconsisting of two neighboring individual layers between them.

The use of metal oxides for the reflection reducing layer does notconstitute an optimal approach so the reflection reducing layer in DE101 31 932 consists of several individual layers of different metalnitrides, whereby the amount of material in a layer is reduced frominitially 100% to 0% and the amount of material in the neighboringindividual layer is increased from 0% to 100% to the same extent.However, it has been found that this layer system also fails to ensurethe desired transmittance.

It has been found that these different layer structures are still toosensitive for climate changes and only special tempering processes aresuitable despite the various measures employed, so that they cannot bemanufactured in a satisfactory quality or yield when there are demandingor definitely different climate conditions.

These layer systems have quality problems in production, even in thecase of raw glass in undefined starting states, i.e., a fluctuatingchemical composition of the glass, in particular with regard to itssodium content. Furthermore, other glass influences such as corrosion orimpressions of the section devices that are used in handling the glassand are often not detectable by visual inspections and cannot beeliminated by the usual cleaning operations, cause unwanted changes inthe properties of the layer system. With such glass influences, it is aparticular disadvantage that their effects on the properties of thelayer system become visible only after the tempering process.

SUMMARY OF THE INVENTION

Therefore an object of the present invention is to provide a layersystem and a method of producing same that will ensure an adequatequality and in particular a high transmittance in the visible range aswell as a low emissivity while at the same time permitting extensivestability of the color locus of the layer system under demanding climateconditions of heat treatment of the substrate and/or undefined states inthe case of the glass substrate.

DETAILED DESCRIPTION OF THE INVENTION

A supplementary underlayer of an oxynitride of a metal, a semiconductoror a semiconductor alloy applied directly to the substrate in aconventional layer sequence which is already reflective for infraredradiation acts as a barrier layer with respect to the substrate bypreventing diffusion processes from the substrate into the layersequence and thus the resulting influences on the layer properties.

When the substrate is glass, this pertains in particular to thediffusion of sodium ions which may be present in differentconcentrations according to the composition of the glass, so thatbecause of these fluctuations, deviations in the color locus may occurwith a layer system and with process conditions that are otherwise thesame after a process that involves the input of heat and thereforetriggers diffusion. In addition, the effects of corrosion of thesubstrate or traces [of substances] on the substrate that have beenformed in previous process sequences in supplying the substrate, e.g.,suction device impressions on glass are suppressed. Effects on theheat-treated layer system arising from these changes in surfaceconditions of the substrate and chemical residues on the substrate canbe suppressed with an inventive underlayer to the extent that a colorvariance remains below a visible limit value.

Since the unwanted diffusion processes due to the input of heat intolayers already deposited may take place, the advantages described herecan also be achieved with layer systems that are not to be tempered whenusing the inventive underlayer.

With the material used here, it is possible that any known low E ortemperable low E layer sequence may be used as the infrared radiationreflecting layer sequence, e.g., a layer sequence from the state of theart as described in the introduction. The layer sequence may thusinclude one or more selective function layers with blocking layersincorporated or embedded in them and additional interface layers as wellas reflection reducing layers formed as a gradient.

Another object of the inventive underlayer is that with the depositionof this supplementary barrier layer, the water entrained by the glasssubstrate into the coating system can be removed from the substratewithout this operation having any effect on the reflective layersequence. In addition to suitability as a barrier layer, the material ofthe inventive underlayer has proven to be much less sensitive to waterthan the materials generally used as an underlayer, e.g., titanium oxide(TiO₂). In addition, such an oxynitride has also proven to beinsensitive in the deposition process, so that the layer properties canalso be adjusted reliably and reproducibly even when there arefluctuating boundary conditions in the manufacturing process.

An effect that is achieved by introducing the barrier layer, consistingof a dielectric material having a low to moderate refraction accordingto this invention, between the substrate and the layer sequence thatreflects infrared radiation is that the optical effect of the inventiveunderlayer is minimized so that the transmittance of the layer sequenceand thus its color locus are subject to little or no change as a resultof the supplementary layer. A layer of low to moderate refraction hereis understood to be a layer having a refractive index such that it is inthe lower range in comparison with the refractive indices of thematerials used in the conventional layer systems that reflect infraredradiation and thus is near the substrate [sic; is near that of thesubstrate]. A refractive index of stoichiometric silicon oxide is knownto be approximately 1.46, which is regarded as being a low refractiveindex, while that of silicon nitride is approximately 2.05, which is ahigh refractive index in comparison with that of materials used forthese layer systems. These refractive indices as well as those givenbelow are always based on the main wavelength of visible light, which is550 nm.

According to an embodiment, the refractive index is approximately equalto or slightly greater than that of the substrate. When the substrate isfloat glass which has a refractive index of approximately 1.52, therefractive index of said inventive underlayer may be 1.50 to 1.85. Inanother embodiment the refractive index of said underlayer is in therange of 1.60 to 1.75. In other embodiments, the refractive index ofthis layer is in the range of 1.50 to 1.60 or in the range of 1.75 to1.85. In either case the refractive index of an oxynitride of a metal,semiconductor or semiconductor alloy can be adjusted very well throughthe oxygen and/or nitrogen content.

An object of the invention is also achieved by another inventive layerwhich concludes the layer system toward the top (as seen from thesubstrate upward) and consists of a dielectric material having a low tomoderate refractive index. This top second layer of dielectric materialwhich has a low to moderate refractive index and, like the bottom layer,consists of an oxynitride of a metal, semiconductor or semiconductoralloy, forms a protective layer for the tempering process.

By means of the adjusted oxygen content, the oxidation of the uppermostlayers of said top layer, which takes places during a tempering processor during the course of use, is reduced and thus color drift is reducedand the transmittance of the layer system is increased so that themechanical and chemical protection of the layer system is ensured due tothe oxygen content of the top layer.

The uppermost layer of a layer sequence that reflects IR radiation isusually a layer of a highly refractive dielectric material that servesas a reflection reducing layer of the layer sequence to improve thetransmittance in the visible range and at the same time serves as a toplayer of the layer sequence to improve its chemical and mechanicalstability. Because of these functions, it usually consists of siliconnitride. In contrast with that, the inventive top layer of the layersystem consists of a material having a low to moderate refractive indexand also containing in addition to a nitrogen component, an adjustableoxygen content. Here again, the possibility of oxynitride is utilized,namely that the refractive index is adjustable, e.g. in a range of 1.50to 1.95, but here in order to achieve an optical effect, namelyoptimization of the reflection reducing function in conjunction with thelayers beneath. In some embodiments the refractive index of this seconddielectric layer having a low to moderate refractive index has a valuebetween 1.50 and 1.60 or between 1.85 and 1.95. In another embodiment,the refractive index of this second dielectric layers amounts between1.60 and 1.85.

It is also possible to combine the inventive underlayer and theinventive top layer in a layer system because of the low or advantageousoptical effect of the layers that supplement the layer sequence andbecause the two layers do not influence one another mutually.

According to the functions described for the first and second dielectriclayers having a medium to low refractive index, they are made of anoxynitride of a metal, a semiconductor or a semiconductor alloy. Becauseof the known properties and the tested manufacturing processes, theinventive underlayer and/or top layer preferably consist of siliconoxynitride. However, oxynitrides of other materials or materialcompositions may also be considered if the respective refractive indexis adjustable and at the same the respective oxygen and nitrogen contentof the two layers are adjustable.

Depending on the mechanical, chemical and optical requirements anddepending on the design of the layer sequences that reflects infraredradiation, the first and second layers which have a low to moderaterefractive index may be made of the same or different materials havingcomparable or different oxygen and/or nitrogen contents or materialshaving approximately the same or different refractive indices.

The starting point for the choice of materials, the optical propertiesand the stoichiometric ratios of the two supplementary layers to beadjusted is always their function as described above and the design ofthe infrared radiation reflecting layer sequence, whereby opticalproperties and stoichiometric ratio may also differ from one anotherwhen using starting materials that are otherwise the same.

According to an embodiment of the present invention, admixtures of othercomponents in one or both supplementary layers, which may be necessaryfor reasons based on the process engineering or in order to achievespecial properties, are also possible. An example that can be mentionedhere is aluminum admixtures, usually in the range between 8% and 15% oreven more or less, or boron doping in the coating source which serves toincrease the efficacy of layer deposition.

The aforementioned properties of the inventive underlayer and top layercan be achieved with the usual layer thicknesses of such systems in therange of a few tens of nanometer, but lower demands are made of thethickness of the underlayer to ensure its barrier function due to theminimized optical influence. Therefore, its optical thickness, which isthe product of the layer thickness and the refractive index, is intendedto be in a relatively large range according to an embodiment of theinvention, namely less than one-eighth of the main wavelength of thespectral range for which the layer system should have the besttransparency. For visible light the wavelength is known to be 550 nm.

To increase the efficacy of the barrier function of the first dielectriclayer having a medium to low refractive index, according to anembodiment of the invention, this layer is deposited as a gradient layerwith an oxygen or nitrogen content that decreases toward the functionlayer. As an alternative or in addition to this or other gradient layersdeposited in the layer sequence, the second dielectric layer which has alow to moderate refractive index and concludes the layer system may bedeposited as a gradient layer with an oxygen or nitrogen content thatdecreases in the direction of the function layer. This embodiment makesit possible to further improve the overall properties of the layersystem.

In this way it is possible to produce a refractive index that changeswith an increase in distance from the layer surface within thesupplementary top layer of the system so that the same stabilizing andreflection reducing effect is achieved as allowed by the sequence of ahighly refractive reflection reducing layer with a top layer arrangedabove having a low to moderate refractive index, so that themanufacturing expense for the layer system can be reduced.

Since both the first and second dielectric layers having a low tomoderate refractive index essentially have little or no influence on thereflection of infrared radiation of the adjacent layer sequence, i.e.,should be added supplementarily, the layer sequence has all theindividual layers that are needed for the desired reflection andtransmittance. Therefore, according to other embodiments, the firstdielectric layer having a low to moderate refractive index is followedby a first dielectric layer having a high refractive index and a seconddielectric layer having a high refractive index is arranged beneath thesecond dielectric layer having a low to moderate refractive index,whereby the refractive index of the first and/or second dielectriclayers having a high refractive index has a value between 1.9 and 2.6 at550 nm. In other embodiments the refractive index of this first and/orsecond dielectric layers has a value between 1.9 and 2.0 or between 2.5and 2.6. In another embodiment, the refractive index of this firstand/or second dielectric layers amounts between 2.0 and 2.5.

Likewise, according to other embodiments, as an alternative or inaddition, the layer sequence may also have one or more blocking layersoptionally also designed as gradient layers or other dielectricinterface layers that stabilize the layer system.

To manufacture the inventive layer system, the first dielectric layerhaving a low to moderate refractive index is deposited by a suitablecoating method directly on the substrate, then the infrared radiationreflecting layer sequence and optionally as an alternative or inaddition to the first layer, the second dielectric layer having a low tomoderate refractive index is also deposited.

A suitable method for manufacturing one or more to all layers would bedirect current (DC) magnetron sputtering or moderate frequency (MF)magnetron sputtering, wherein the oxynitrides, oxides and/or nitridesare applied by reactive coating from a metallic or semiconductingcoating source as well as in a nonreactive or partially reactive coatingprocess from such a coating source consisting of the stoichiometric orsubstoichiometric oxide or nitride of the layer material.

In another embodiment the first or second dielectric layer or the firstand second dielectric layers having a low to moderate refractive indexare applied by a chemical vapor deposition process (CVD) or a plasmasupported CVD process. This layer thickness which can be producedinaccurately by these methods is accepted because in the case of thesetwo layers it has little or no influence on the infrared radiationreflecting property of the layer system. Instead, however, layersproduced by this chemical method have especially good barrier propertiesand thus have locus and transmittance stabilizing properties.

Like the fluctuations in layer thickness, admixtures in the material areharmless for the manufacturing process for the two supplementary layers.For the production of certain geometries of coating sources, e.g., oftubular cathodes, for example, or to increase the electric conductivityof the coating material, it is possible to add aluminum with admixturesof much less than 20% or to perform boron doping. Other admixtures forother purposes are also possible.

The present invention will now be explained in greater detail on thebasis of one exemplary embodiment shown in the FIGURE. The respectivedrawing shows in the FIGURE an inventive layer system on a substrate offloat glass. The individual layers of the layer system described beloware arranged one above the other starting from the glass substrate.

The first dielectric layer 1 having a low to moderate refractive indexand consisting of substoichiometric silicon oxynitride (SiO_(x)N_(y)) isarranged directly on the substrate S made of float glass. It functionsas a barrier layer for diffusing sodium ions of the glass into the layersystem and at the same time has adhesive properties for the subsequentlayer.

This is followed by the first highly refractive dielectric layer 2 whichalso serves as an adhesive and at the same time improves the mechanicaland chemical properties of the system as a whole. In the exemplaryembodiment described here, it consists of TiO₂.

The first blocking layer 3 applied thereto consists of substoichiometricNiCrO_(x). This is followed by the first interface layer 4 ofsubstoichiometric zinc aluminum oxide (hereinafter referred to asZnAlO_(x)) which in particular improves the adhesion of the followingselective function layer 5. The following selective function layer 5consists of silver and is covered with another interface layer 6, namelythe second interface layer made of the same material as the firstinterface layer 4. The second interface layer 6 is in turn covered by asecond blocking layer 7 which is also made of substoichiometricNiCrO_(x), like the first blocking layer 3. As an alternative, thesecond interface layer 6 may also be omitted.

The third interface layer 8 which follows the second blocking layer 7 inthe exemplary embodiment and consists of stoichiometric tin oxide (SnO₂)in the exemplary embodiment is optional. In the exemplary embodimentthis third interface layer 8 was inserted to improve the mechanicalstability, i.e., the abrasion resistance of the system by reducing layerstresses which occur in particular with silicon nitride.

This layer sequence 11 which is deposited above the first dielectriclayer 1 having a low to moderate refractive index, wherein this is alow-E layer sequence in the exemplary embodiment, is covered by atraditional top layer which serves in particular as the reflectionreducing layer and is made of a highly refractive dielectric material 9that contains silicon, namely Si₃N₄ in the present exemplary embodiment.

The top layer covering the inventive layer system is the seconddielectric layer 10 having a low to moderate refractive index. Like thefirst dielectric layer, this dielectric layer also consists ofsubstoichiometric silicon oxynitride, but with a different oxygen andnitrogen content (SiO_(v)N_(w)). It is possible that the oxygen andnitrogen content or the oxygen or the nitrogen content of the firstdielectric layer 1 having a low to moderate refractive index differsfrom the oxygen and/or nitrogen content of the second dielectric layer10 having a low to moderate refractive index. In the exemplaryembodiment the oxygen content “v” is lower in comparison with that ofthe first dielectric layer 1, i.e., “x” having a low to moderaterefractive index.

Such a layer system is manufactured in a known way in a coatinginstallation having a plurality of coating stations that follow oneanother and where the individual layers are deposited one after theother by suitable vacuum coating processes, namely in the present caseby medium frequency (MF) sputtering, onto a planar cleaned substrate Sfrom a metallic or semimetallic coating source in the presence of aninert gas such as argon and in the case of layers containing oxygen ornitrogen with the additional presence of oxygen or nitrogen as areactive gas.

To produce one or more of the dielectric layers 1, 10, 2, 9 that have alayer composition that changes continuously and have a low to moderaterefractive index or a high refractive index or to produce the blockinglayers 3, 7 as gradient layers, the layers are deposited in thecorresponding coating station(s) by means of a spatial arrangement ofone or more coating sources using a different material or the samematerial and using a different gas inlet into the coating station.

We claim:
 1. Method for manufacturing an infrared radiation reflectingtransparent layer system in which an infrared radiation reflecting layersequence is deposited by vacuum coating on a transparent substrate, saidlayer sequence consisting of, as seen from the substrate upward, a. afirst transparent dielectric layer of an oxynitride of a metal, asemiconductor or a semiconductor alloy having a low to moderaterefractive index; b. a second transparent dielectric layer having a highrefractive index; c. a blocking layer; d. a first interface layer; e. aselective function layer; f. an optionally present second interfacelayer; g. a second blocking layer; h. an optionally present thirdinterface layer; i. a third transparent dielectric layer having a highrefractive index and containing silicon; and j. a fourth transparentdielectric layer of an oxynitride of a metal, a semiconductor or asemiconductor alloy having a low to moderate refractive index.
 2. Methodaccording to claim 1, wherein the refractive index of said firstdielectric layer having a low to moderate refractive index isapproximately equal to or slightly greater than the refractive index ofthe substrate.
 3. Method according to claim 2, wherein the refractiveindex of said first dielectric layer having a low to moderate refractiveindex is in the range between 1.50 and 1.85 at a main wavelength ofvisible light of approximately 550 nm.
 4. Method according to claim 1,wherein the refractive index of said fourth dielectric layer having alow to moderate refractive index is between 1.50 and 1.95 at a mainwavelength of visible light of approximately 550 nm.
 5. Method accordingto claim 1, wherein said first and fourth dielectric layers having a lowto moderate refractive index have approximately the same refractiveindex.
 6. Method according to claim 1, wherein the refractive index ofat least one of said second and third highly refractive dielectriclayers amounts to approximately 1.9 to 2.6 with light of a wavelength of550 nm.
 7. Method according to claim 1, wherein an oxynitride of siliconis deposited as at least one of said first and fourth dielectric layershaving a low to moderate refractive index.
 8. Method according to claim7, wherein said first dielectric layer having a low to moderaterefractive index is deposited with an oxygen and nitrogen content thatdiffers from the oxygen and nitrogen content of said fourth dielectriclayer having a low to moderate refractive index.
 9. Method according toclaim 7, wherein said first dielectric layer having a low to moderaterefractive index is deposited with an oxygen or nitrogen content thatdiffers from the oxygen or nitrogen content of said fourth dielectriclayer having a low to moderate refractive index.
 10. Method according toclaim 1, wherein at least one of said first and fourth dielectric layershaving a low to moderate refractive index is applied by chemical vapordeposition methods (CVD methods) or plasma-supported CVD processes. 11.Method according to claim 1, wherein at least one of said first andfourth dielectric layers having a low to moderate refractive index isapplied by reactive magnetron sputtering of silicon or silicon-aluminumalloys in an atmosphere containing at least one of the gases oxygen andnitrogen.
 12. Method according to claim 1, wherein at least one of saidfirst and fourth dielectric layers having a low to moderate refractiveindex is deposited as a gradient layer with an oxygen and nitrogencontent that decreases toward the function layer.
 13. Method accordingto claim 1, wherein a transparent second dielectric layer of an oxide ornitride of a metal, a semiconductor or a semiconductor alloy having ahigh refractive index is deposited directly as a bottom layer of saidlayer sequence on said first dielectric layer having a low to moderaterefractive index.
 14. Method according to claim 1 wherein said layersequence consists of: a. silicon oxynitride; b. titanium oxide; c.nickel chromium oxide; d. zinc aluminum oxide; e. silver; f. optionallypresent zinc aluminum oxide; g. nickel chromium oxide; h. optionallypresent stannic oxide; i. silicon nitride; and j. silicon oxynitride.